CN116179234B - Method for preparing aromatic hydrocarbon-rich biological oil by collaborative pyrolysis of biomass and waste plastics - Google Patents
Method for preparing aromatic hydrocarbon-rich biological oil by collaborative pyrolysis of biomass and waste plastics Download PDFInfo
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- CN116179234B CN116179234B CN202310323281.3A CN202310323281A CN116179234B CN 116179234 B CN116179234 B CN 116179234B CN 202310323281 A CN202310323281 A CN 202310323281A CN 116179234 B CN116179234 B CN 116179234B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
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- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The application discloses a method for preparing aromatic hydrocarbon-rich biological oil by collaborative pyrolysis of biomass and waste plastics, which adopts a zinc and aluminum co-modified micropore-mesopore composite molecular sieve catalyst, and can effectively improve the aromatic hydrocarbon ratio in pyrolysis oil and reduce the yield of oxygen-containing compounds by utilizing a bimetallic composite molecular sieve catalyst. The method can effectively improve the quality of the biological oil, control the content of the oxygen-containing compound to be below 10%, greatly increase the content of aromatic hydrocarbon in the biological oil and effectively promote the industrialization progress of the co-pyrolysis process. The product distribution of the pyrolysis oil is directionally regulated and controlled by an in-situ catalytic pyrolysis method, so that the recycling utilization of the organic solid wastes is realized, the biomass and waste plastics are promoted to directionally pyrolyze and prepare the aromatic hydrocarbon-rich biological oil, the quality of the biological oil can be improved while the recycling utilization of the organic solid wastes (agriculture and forestry wastes and plastic wastes) is realized, and the industrialized application of the biomass pyrolysis liquefaction technology is promoted.
Description
Technical Field
The application belongs to the technical field of biomass energy thermal conversion utilization, and particularly relates to a method for preparing aromatic hydrocarbon-rich bio-oil by collaborative pyrolysis of biomass and waste plastics.
Background
Energy is an important material basis for human survival and development, and excessive use of fossil energy causes problems of global warming, environmental pollution, energy crisis and the like. Biomass energy is an important energy strategic reserve in China, and is the only carbon-based renewable energy source which can be directly converted into liquid fuel. Aromatic hydrocarbons are important basic chemicals for organic chemical industry, and are widely applied to various fields such as biofuel, energy storage materials, composite materials, additives and the like, and the preparation method is mainly from petrochemical industry. The direct catalytic pyrolysis of biomass to liquid aromatic hydrocarbon to obtain high-value products is an effective means for improving the energy density and stability of biological oil, and is also an important way for relieving energy shortage and reducing greenhouse gas emission.
However, due to the effective hydrogen content (H/C eff The= (H-2O)/C, 0-0.5) is generally lower, the bio-oil prepared by catalytic pyrolysis still has the problems of low energy density, poor stability, low target product selectivity and the like, and the catalyst is easy to be subjected to carbon deposition deactivation, so that the aromatic hydrocarbon yield is lower. Molecular sieve catalysts are mostly used in experiments for preparing hydrocarbon-rich bio-oil by catalyzing biomass directional pyrolysis, but have some problems in practical application: the method is easy to cause low conversion rate of raw materials and deactivation of the catalyst, and has low acid strength and poor hydrothermal stability.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the application and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description of the application and in the title of the application, which may not be used to limit the scope of the application.
The present application has been made in view of the above and/or problems occurring in the prior art.
Therefore, the application aims to overcome the defects in the prior art and provide a method for preparing aromatic hydrocarbon-rich bio-oil by the co-pyrolysis of biomass and waste plastics.
In order to solve the technical problems, the application provides the following technical scheme: a method for preparing aromatic hydrocarbon-rich bio-oil by co-pyrolysis of biomass and waste plastics is characterized by comprising the following steps: comprises that a microporous-mesoporous composite molecular sieve catalyst is adopted to promote the directional pyrolysis of biomass and waste plastics to prepare aromatic hydrocarbon-rich biological oil, and the aromatic hydrocarbon ratio in the biological oil prepared by the collaborative pyrolysis of the biomass and the waste plastics is improved.
As a preferred embodiment of the preparation process according to the application, there is provided: the composite molecular sieve catalyst is ZSM-5/MCM-41 composite molecular sieve.
As a preferred embodiment of the preparation process according to the application, there is provided: the ZSM-5/MCM-41 composite molecular sieve adopts zinc and aluminum for co-modification.
As a preferred embodiment of the preparation process according to the application, there is provided: in the zinc and aluminum co-modification process, the mass ratio of Zn to Al is 3:1, 2:2 or 1:3.
As a preferred embodiment of the preparation process according to the application, there is provided: the granularity of the biomass and the waste plastic is 40-120 meshes.
As a preferred embodiment of the preparation process according to the application, there is provided: the mass ratio of biomass to waste plastic in the raw materials is 4:1 to 1:4.
as a preferred embodiment of the preparation process according to the application, there is provided: the mass ratio of the raw materials to the catalyst is 1:1 to 10.
As a preferred embodiment of the preparation process according to the application, there is provided: the directional pyrolysis adopts a double-click type thermal cracker, the temperature of a reaction zone is 550-650 ℃, and the reaction time is 5-20 s.
As a preferred embodiment of the preparation process according to the application, there is provided: the biological oil prepared by the preparation method has the oxygen-containing compound accounting for less than 10 percent.
The application has the beneficial effects that:
(1) The bimetallic composite molecular sieve catalyst can effectively improve the aromatic hydrocarbon ratio in pyrolysis oil, reduce the yield of oxygen-containing compounds, and increase the increment of aromatic hydrocarbon by 30.16 percent at most.
(2) The experimental method can effectively improve the quality of the biological oil, control the oxygen-containing compound to be less than 10%, greatly increase the aromatic hydrocarbon content in the biological oil and effectively promote the industrialization progress of the co-pyrolysis process.
(3) Organic solid waste (agricultural and forestry waste and plastic waste) is fully utilized, and the product distribution of pyrolysis oil is directionally regulated and controlled by an in-situ catalytic pyrolysis method, so that the recycling utilization of the organic solid waste is realized.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is a schematic flow chart of the production mode of the application.
Detailed Description
In order that the above-recited objects, features and advantages of the present application will become more apparent, a more particular description of the application will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application, but the present application may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present application is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the application. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
Preparing 100mL of NaOH solution with the concentration of 2mol/L, putting a ZSM-5 catalyst with the silicon-aluminum ratio of 50 into the solution for dissolution, and magnetically stirring for 2h to obtain 3mol/L Al 2 O 3 ·SiO 2 A solution. Then, 125mL of 10wt% template cetyl trimethyl ammonium bromide was added, and the mixture was magnetically stirred for 2 hours and then placed in a 105 ℃ oven for crystallization for 25 hours. The solution was taken out and cooled to room temperature, the pH of the solution was adjusted to 8.5, and then placed in a 105℃oven for crystallization for 25h. Taking out the crystallized substances, washing, filtering, and putting into a 105 ℃ oven for drying for 15 hours. The catalyst is put into a tubular furnace with 550 ℃ air atmosphere for roasting for 5 hours, and then 200mL of NH with the concentration of 1.0mol/L is put into 4 The solution was stirred for 3h for ion exchange. And then washing, filtering, drying at 105 ℃ for 2 hours and roasting at 550 ℃ for 2 hours to prepare the ZSM-5/MCM-41 composite molecular sieve.
Example 2
Two metals Zn and Al are jointly loaded on a microporous-mesoporous molecular sieve ZSM-5/MCM-41 according to the mass ratio of 3:1, 2:2 and 1:3, and 3Zn1Al represents 3wt.% Zn and 1wt.% Al is loaded on the ZSM-5/MCM-41. Zn (NO) 3 ) 2 And Al (NO) 3 ) 3 Mixing with deionized water, adding ZSM-5/MCM-41, stirring at 30deg.C for 10 hr, oven drying in a oven (105deg.C) for 12 hr, and oven drying in a muffle furnace (550deg.C) for 5 hr.
Table 1 characteristics of the catalyst
Example 3
The biomass and the polypropylene waste plastics are crushed to be below 80 meshes, the biomass and the waste plastics are ground in a mortar according to a mass ratio of 1:1 for 5min until the color is uniform, then the mixture is pressed into tablets and ground again, and the biomass and the waste plastics are mixed uniformly according to the step. Then grinding catalysts (ZSM-5/MCM-41, 3Zn1Al-ZSM-5/MCM-41, 2Zn2Al-ZSM-5/MCM-41 and 1Zn3 Al-ZSM-5/MCM-41) with raw materials (biomass and waste plastics) according to a mass ratio of 10:1 in a mortar for 5min until the colors are uniform, and then tabletting and regrinding the mixture, thus obtaining the catalytic sample three times according to the step.
Example 4
Uniformly mixing corn straw and polypropylene (the grain size of the raw materials is smaller than 80 meshes) according to the mechanical mixing method, placing the mixture in a sample cup of a thermal cracker, pushing the sample into the reaction zone for pyrolysis for 10s when the temperature of the reaction zone is raised to 600 ℃, and analyzing the composition of pyrolysis products on line, wherein the content of aromatic hydrocarbon is 0%.
Example 5
After uniformly mixing corn straw and polypropylene according to the mass ratio of 1:1, uniformly mixing a mixed sample and a ZSM-5/MCM-41 catalyst according to the mass ratio of 1:10, placing a catalytic sample into a sample cup of a thermal cracker, pushing the sample into the reaction zone for pyrolysis for 10s when the temperature of the reaction zone is raised to 600 ℃, and analyzing the composition of pyrolysis products on line, wherein the proportion of aromatic hydrocarbon is 15.12%.
Example 6
After uniformly mixing corn straw and polypropylene according to the mass ratio of 1:1, uniformly mixing a mixed sample with catalysts (3 Zn1Al-ZSM-5/MCM-41, 2Zn2Al-ZSM-5/MCM-41 and 1Zn3 Al-ZSM-5/MCM-41) according to the mass ratio of 1:10, placing the catalytic sample in a sample cup of a thermal cracker, heating the reaction zone to 600 ℃, pushing the sample into the reaction zone for pyrolysis for 10 seconds, and analyzing the composition of pyrolysis products on line, wherein the proportion of aromatic hydrocarbon is 18.01%, 23.33% and 30.16% under the action of the three catalysts.
Wherein, the benzene content is 1.03, 1.23 and 1.35 times of the benzene content in the catalysis of ZSM-5/MCM-41; toluene content is 1.10, 1.69 and 1.87 times of that of ZSM-5/MCM-41 during catalysis; the content of the dimethylbenzene is 1.36 times, 1.82 times and 2.36 times of that of the dimethylbenzene during the catalysis of ZSM-5/MCM-41; the content of trimethylbenzene is 0.76, 0.88 and 1.21 times of that of ZSM-5/MCM-41 during catalysis; naphthalene content is 0.82, 0.93 and 1.23 times of that of ZSM-5/MCM-41 during catalysis; the indene content is 0.77, 1.13 and 1.10 times of that of ZSM-5/MCM-41 during catalysis.
When ZSM-5/MCM-41 catalyzes corn stalk and polypropylene, the content of aromatic hydrocarbon is 15.12%, and when 4Zn-ZSM-5/MCM-41 and 4Al-ZSM-5/MCM-41 are adopted for experiments, the content of aromatic hydrocarbon is 12.16% and 13.39%. When the 4Zn-ZSM-5/MCM-41 is adopted for experiments, the contents of benzene, toluene, dimethylbenzene, trimethylbenzene, naphthalene and indene are respectively 0.51, 0.59, 0.76, 0.42, 0.31 and 0.26 times of those of the catalyst used for ZSM-5/MCM-41 catalysis; when the experiment is carried out by adopting 4Al-ZSM-5/MCM-41, the contents of benzene, toluene, dimethylbenzene, trimethylbenzene, naphthalene and indene are respectively 0.78 times, 0.81 times, 0.89 times, 0.69 times, 1.02 times and 0.53 times of the contents of the benzene, the toluene, the dimethylbenzene, the trimethylbenzene, the naphthalene and the indene when the ZSM-5/MCM-41 is catalyzed.
Through the above examples, the inventors found that when the experiments were conducted using separate Zn or Al modified catalysts of 4Zn-ZSM-5/MCM-41 and 4Al-ZSM-5/MCM-41, the aromatic hydrocarbon content was lower than when the experiments were conducted using the catalyst ZSM-5/MCM-41 without metal modification, because the Zn loading reduced the specific surface area, pore volume, acid content of the catalyst and increased the pore diameter; the loading of Al reduces the specific surface area and pore volume of the catalyst, and increases the pore diameter and acid quantity, so that the Zn or Al independently modified catalyst is not higher than the aromatic hydrocarbon content in the unmodified catalyst, and the Zn and Al added in the application have synergistic effect.
The smaller the particle size, the better the mixing effect of biomass and plastic, but the smaller the particle size, the more energy consumption is, and the reaction rate is reduced when the particle size is too large, so the inventor obtains 80 meshes as the best choice through experiments;
biomass pyrolysis produces three-phase products of gas, liquid, and solid, while bio-oil is a liquid product, with more gaseous products when the temperature is higher and more solid products when the temperature is lower. That is, the total sum of the three-phase products is constant in terms of mass conservation, and the inventors conducted experiments at 285, 345, 445, 500, 600, 700℃pyrolysis temperatures, where the pyrolysis time was the same, and the total peak areas of the respective temperatures were 1.09X 10, respectively 7 、5.11×10 7 、1.31×10 8 、1.43×10 8 、1.80×10 8 And 8.39X10 7 Therefore, it is preferable that the yield of bio-oil is highest at 600 ℃;
the pyrolysis time has less effect on the pyrolysis product distribution, and the total peak areas for pyrolysis of 1,5, 10, 20s of the raw materials are respectively 4.81×10 at the preferred pyrolysis temperature 7 、1.29×10 8 、1.43×10 8 、1.09×10 8 The bio-oil yield was found to be highest at 10s pyrolysis.
It should be noted that the above embodiments are only for illustrating the technical solution of the present application and not for limiting the same, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present application may be modified or substituted without departing from the spirit and scope of the technical solution of the present application, which is intended to be covered in the scope of the claims of the present application.
Claims (3)
1. A method for preparing aromatic hydrocarbon-rich bio-oil by co-pyrolysis of biomass and waste plastics is characterized by comprising the following steps: comprising the steps of (a) a step of,
crushing biomass and waste plastics, mixing with a micro-mesoporous composite molecular sieve catalyst, and directionally pyrolyzing to prepare aromatic hydrocarbon-rich biological oil;
the micro-mesoporous composite molecular sieve catalyst is a ZSM-5/MCM-41 composite molecular sieve;
the ZSM-5/MCM-41 composite molecular sieve adopts zinc and aluminum for co-modification;
the directional pyrolysis adopts a double-click type thermal cracker, the temperature of a reaction zone is 600 ℃, and the reaction time is 10s;
in the zinc and aluminum co-modification process, the mass ratio of Zn to Al is 1:3, a step of;
the mass ratio of the biomass to the waste plastic is 4: 1-1: 4, a step of;
the mass ratio of the biomass waste plastic to the catalyst is 1: 1-10.
2. The method for preparing aromatic-rich bio-oil according to claim 1, wherein: the biomass and the waste plastics are crushed, wherein the granularity of the biomass and the waste plastics is 40-120 meshes.
3. The method for preparing aromatic-rich bio-oil according to claim 1, wherein: the content of the oxygen-containing compound in the aromatic hydrocarbon-rich biological oil is lower than 10 percent.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103920526A (en) * | 2014-04-30 | 2014-07-16 | 清华大学 | Composite catalyst for catalytic pyrolysis preparation of aromatic hydrocarbon and preparation method of composite catalyst |
| CN105175205A (en) * | 2015-07-14 | 2015-12-23 | 南京林业大学 | Method for preparing aromatic hydrocarbon through catalytic aromatization of carboxylic acid methyl ester prepared from biomass oil |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103920526A (en) * | 2014-04-30 | 2014-07-16 | 清华大学 | Composite catalyst for catalytic pyrolysis preparation of aromatic hydrocarbon and preparation method of composite catalyst |
| CN105175205A (en) * | 2015-07-14 | 2015-12-23 | 南京林业大学 | Method for preparing aromatic hydrocarbon through catalytic aromatization of carboxylic acid methyl ester prepared from biomass oil |
Non-Patent Citations (3)
| Title |
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| Biofuel production from distillers dried grains with solubles (DDGS) co-fed with waste agricultural plastic mulching films via microwave-assisted catalytic fast pyrolysis using microwave absorbent and hierarchical ZSM-5/ MCM-41 catalyst;Bo Zhang等;Journal of Analytical and Applied Pyrolysis;第1-7页 * |
| Bo Zhang等.Biofuel production from distillers dried grains with solubles (DDGS) co-fed with waste agricultural plastic mulching films via microwave-assisted catalytic fast pyrolysis using microwave absorbent and hierarchical ZSM-5/ MCM-41 catalyst.Journal of Analytical and Applied Pyrolysis.2018,第1-7页. * |
| Catalytic co-pyrolysis of corn stalk and polypropylene over Zn-Al modifed MCM-41 catalysts for aromatic hydrocarbon-rich oil production;Tanglei Sun等;Industrial Crops & Products;第1-12页 * |
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